US7157473B2ExpiredUtilityA1

Pyridyl substituted heterocycles useful for treating or preventing HCV infection

81
Assignee: RIGEL PHARMACEUTICALS INCPriority: Aug 23, 2002Filed: Aug 22, 2003Granted: Jan 2, 2007
Est. expiryAug 23, 2022(expired)· nominal 20-yr term from priority
A61P 31/12C07D 413/04C07D 401/04C07D 401/14C07D 413/14C07D 417/04A61P 1/16C07D 417/14
81
PatentIndex Score
12
Cited by
66
References
57
Claims

Abstract

The present invention relates to pyridyl substituted heterocycles and hydro isomers thereof and pharmaceutical compositions thereof that inhibit replication and/or proliferation of HCV virus. The present invention also relates to the use of the pyridyl heterocycles and hydro isomers thereof and/or pharmaceutical compositions comprising the compounds to treat or prevent HCV infections.

Claims

exact text as granted — not AI-modified
1. A compound according to structural formula (I) or (II): 
       
         
           
           
               
               
           
         
         or a pharmaceutically acceptable salt, hydrate, solvate or N-oxide thereof, wherein: 
         the B ring is an aromatic or nonaromatic ring that includes from one to four heteroatoms, wherein 
         X, Y, and Z are each, independently of one another selected from C, CH, N, NR 16 , NR 18 , S or O, provided that X and Y are not both O; 
         U and T are each, independently of one another, selected from C, or CH; 
         A is N or —CR 2 —; 
         B is N or —CR 3 —; 
         D is N or —CR 4 —; 
         E is N or —CR 5 —; 
         G is N or —CR 6 —; 
         J is N or —CR 8 —; 
         K is N or —CR 8 —; 
         L is N or —CR 9 —; 
         M is N or —CR 10 —; 
         R 2  and R 6  are each, independently of one another, selected from the group consisting of hydrogen, halo, C 1 –C 15  alkyl, substituted C 1 –C 15  alkyl, alkylthio, substituted C 1 –C 15  alkylthio, alkoxy, substituted alkoxy, alkoxycarbonyl, substituted alkoxycarbonyl, C 1 –C 15  arylalkyloxycarbonyl, substituted aryl-C 1 –C 15  arylalkyloxycarbonyl, aryloxycarbonyl, substituted aryloxycarbonyl, cycloheteroalkyl, substituted cycloheteroalkyl, carbamoyl, substituted carbamoyl, halo-C 1 –C 15  alkyl, sulfamoyl, substituted sulfamoyl and silyl ethers, provided that one of R 2  and R 6  is other than hydrogen; 
         R 3  and R 5  are each, independently of one another, selected from the group consisting of hydrogen, halo, C 1 –C 15  alkyl, substituted C 1 –C 15  alkyl, C 1 –C 15  alkylthio, substituted C 1 –C 15  alkylthio, alkoxy, substituted alkoxy, alkoxycarbonyl, substituted alkoxycarbonyl, aryl-C 1 –C 15  arylalkyloxycarbonyl, substituted aryl-C 1 –C 15  alkyloxycarbonyl, aryloxycarbonyl, substituted aryloxycarbonyl, cycloheteroalkyl, substituted cycloheteroalkyl, carbamoyl, substituted carbamoyl, halo-C 1 –C 15  alkyl, sulfamoyl and substituted sulfamoyl; 
         R 4  is selected from the group consisting of hydrogen, halo, C 1 –C 15  alkyl, substituted C 1 –C 15  alkyl, C 1 –C 15  alkylthio, substituted C 1 –C 15  alkylthio, carbamoyl, substituted carbamoyl, alkoxy, substituted alkoxy, alkoxycarbonyl, substituted alkoxycarbonyl, aryl-C 1 –C 15  alkyloxycarbonyl, substituted aryl-C 1 –C 15  alkyloxycarbonyl, aryloxycarbonyl, substituted aryloxycarbonyl, di-C 1 –C 15  alkylamino, substituted di-C 1 –C 15  alkylamino, halo-C 1 –C 15  alkyl, sulfamoyl and substituted sulfamoyl; 
         R 7  is —NR 11 C(O)R 12 ; 
         R 8 , R 9 , R 10  and R 14  are each, independently of one another, hydrogen, halo or fluoro; 
         R 11  is hydrogen, or C 1 –C 15  alkyl; and 
         R 12  is selected from the group consisting of substituted C 1 –C 15  alkyl, halo-C 1 –C 15  alkyl, cycloheteroalkyl and substituted cycloheteroalkyl; 
         R 16  and R 18  are each, independently of one another, selected from the group consisting of hydrogen, lower alkyl, substituted lower alkyl, lower heteroalkyl, substituted lower heteroalkyl, cycloalkyl, substituted cycloalkyl, cycloheteroalkyl, substituted cycloheteroalkyl, lower haloalkyl, lower alkylthio, substituted lower alkylthio, lower alkoxy, substituted lower alkoxy, methoxy, substituted methoxy, lower heteroalkoxy, substituted lower heteroalkoxy, cycloalkoxy, substituted cycloalkoxy, cycloheteroalkoxy, substituted cycloheteroalkoxy, lower haloalkoxy, monohalomethoxy, dihalomethoxy, trihalomethoxy, trifluoromethoxy, lower di- or monoalkylamino, substituted lower di- or monoalkylamino, aryl, substituted aryl, aryloxy, substituted aryloxy, phenoxy, substituted phenoxy, aryl-C 1 –C 15  alkyl, substituted aryl-C 1 –C 15  alkyl, aryl-C 1 –C 15  alkyloxy, substituted aryl-C 1 –C 15  alkyloxy, benzyl, benzyloxy, heteroaryl, substituted heteroaryl, heteroaryloxy, substituted heteroaryloxy, heteroaryl-C 1 –C 15  alkyl, substituted heteroaryl-C 1 –C 15  alkyl, heteroaryl-C 1 –C 15  alkyloxy, substituted heteroaryl-C 1 –C 15  alkyloxy, carboxyl, lower alkoxycarbonyl, substituted lower alkoxycarbonyl, aryloxycarbonyl, substituted aryloxycarbonyl, aryl-C 1 –C 15  alkyloxycarbonyl, substituted aryl-C 1 –C 15  alkyloxycarbonyl, carbamate, substituted carbamate, carbamoyl, substituted carbamoyl, sulfamoyl, substituted sulfamoyl and a group of the formula -L-R 17 , where “L” is a linker and R 17  is cycloalkyl, substituted cycloalkyl, cycloheteroalkyl or substituted cycloheteroalkyl 
         with the provisos that:
 (i) at least one of A, B, D, E, G, J, K, L or M is N; 
 (ii) no more than one of A, B, D, E or G is N; and 
 (iii) no more than one of J, K, L or M is N. 
 
       
     
     
       2. The compound of  claim 1  in which one of A, B, D, E or G is N and one of J, K, L or M is N. 
     
     
       3. The compound of  claim 1  in which one of A, B, D, E or G is N and none of J, K, L or M is N. 
     
     
       4. The compound of  claim 1  in which none of A, B, D, E or G is N and one of J, K, L or M is N. 
     
     
       5. The compound of  claim 1  in which the B-ring is an oxazole or hydro isomer thereof. 
     
     
       6. The compound of  claim 1  in which the B ring is a thiazole or a hydro isomer thereof. 
     
     
       7. The compound of  claim 1  in which the B ring is an imidazoleor a hydro isomer thereof. 
     
     
       8. The compound of  claim 1  in which the B ring is a triazole or a hydro isomer thereof. 
     
     
       9. The compound of  claim 1  in which the B ring is an oxadiazole or a hydro isomer thereof. 
     
     
       10. The compound of  claim 1  in which the B ring is an isoxazole or a hydro isomer thereof. 
     
     
       11. The compound of  claim 1  in which the B ring is a pyrazole or a hydro isomer thereof. 
     
     
       12. The compound of  claim 1  in which the B ring is a thiadiazole or a hydro isomer thereof. 
     
     
       13. The compound of any one of  claims 1 – 12  in which R 7  is —NR 11 C(O)R 12 , wherein R 11  is hydrogen or methyl and R 12  is —CHCl 2 . 
     
     
       14. The compound of  claim 13  in which X is N, Y is O and Z is —CH—. 
     
     
       15. The compound of  claim 1  in which A is —CR 2 —, G is —CR 6 —, R 7  is —NR 11 C(O)R 12 , where R 11  is hydrogen or methyl and R 12  is —CHCl 2 . 
     
     
       16. The compound of  claim 15  in which B is —CR 3 —, D is N, E is —CR 5 —, J is —CR 14 —, K is —CR 8 —, L is —CR 9 —, M is —CR 10 —, and R 3 , R 5 , R 9 , R 10  and R 14  are each hydrogen. 
     
     
       17. The compound of  claim 16  in which R 8  is fluorine. 
     
     
       18. The compound of  claim 15  in which B is —CR 3 —, D is —CR 4 —, E is —CR 5 —, J is —CR 14 —, K is —CR 8 —, L is —CR 9 —, M is N and R 3 , R 4 , R 5 , R 8 , R 9  and R 14  are each hydrogen. 
     
     
       19. The compound of  claim 15  in which B is —CR 3 —, D is —CR 4 —, E is —CR 5 —, J is —CR 14 —, K is —CR 8 —, L is N, M is —CR 10 — and R 3 , R 4 , R 5 , R 8 , R 10  and R 14  are each hydrogen. 
     
     
       20. The compound of any one of  claims 15 – 19  in which R 2  and R 6  are each, independently of one another, selected from the group consisting of chloro, fluoro, methyl, triflouromethyl, thiomethyl, methoxy, i-propoxy, N-morpholino and N-morpholinosulfamoyl. 
     
     
       21. The compound of any one of  claims 15 – 19  in which R 2  and R 6  are each, independently of one another, selected from the group consisting of chloro, fluoro, methyl, triflouromethyl, methoxy or i-propoxy. 
     
     
       22. The compound of any one of  claims 15 – 19  in which R 2  and R 6  are each the same or different halo. 
     
     
       23. The compound of any one of  claims 15 – 19  in which X is N, Y is O and Z is —CH—. 
     
     
       24. The compound of  claim 1  in which A is —CR 2 —, G is —CR 6 — and R 7  is —NR 11 C(O)R 12 , where R 11  is hydrogen or methyl and R 12  is —CH 2 I. 
     
     
       25. The compound of  claim 24  in which R 2  and R 6  are each, independently of one another, selected from the group consisting of chloro, fluoro, methyl, triflouromethyl, thiomethyl, methoxy, i-propoxy, N-morpholino and N-morpholinosulfamoyl. 
     
     
       26. The compound of  claim 24  in which R 2  and R 6  are each, independently of one another, selected from the group consisting of chloro, fluoro, methyl, triflouromethyl, methoxy and i-propoxy. 
     
     
       27. The compound of  claim 24  in which R 2  and R 6  are each the same or different halo. 
     
     
       28. The compound of  claim 24  in which X is N, Y is O and Z is —CH—. 
     
     
       29. The compound of  claim 1  in which A is —CR 2 —, B is —CR 3 —, R 7  is —NR 11 C(O)R 12 , where R 11  is hydrogen or methyl and R 12  is —CHCl 2 . 
     
     
       30. The compound of  claim 29  in which D is —CR 4 —, G is —CR 6 —, E is —CR 5 —, J is —CR 14 —, K is —CR 8 —, L is —CR 9 —, M is N and R 4 , R 5 , R 6 , R 8 , R 9  and R 14  are each hydrogen. 
     
     
       31. The compound of  claim 29  in which D is —CR 4 —, G is —CR 6 —, E is —CR 5 —, J is —CR 4 —, K is —CR 8 —, L is N, M is —CR 10 — and R 4 , R 5 , R 6 , R 8 , R 10  and R 14  are each hydrogen. 
     
     
       32. The compound of any one of  claims 29 – 31  in which R 2  is chloro, fluoro, methyl, triflouromethyl, thiomethyl, methoxy, i-propoxy, N-morpholino or N-morpholinosulfamoyl and R 3  is chloro, fluoro, methyl, triflouromethyl or methoxy. 
     
     
       33. The compound of any one of  claims 29 – 31  in which R 2  is chloro, fluoro, methyl, triflouromethyl or methoxy and R 3  is chloro, fluoro or triflouromethyl. 
     
     
       34. The compound of any one of  claims 29 – 31  in which R 2  and R 3  are each the same or different halo. 
     
     
       35. The compound of any one of  claims 29 – 31  in which X is N, Y is O and Z is —CH—. 
     
     
       36. The compound of  claim 1  in which A is —CR 2 —, G is —CR 6 — and R 2  and R 6  are each identical, provided that R and R 6  are not hydrogen. 
     
     
       37. The compound of  claim 1  in which A is —CR 2 —, B is —CR 3 — and R 2  and R 3  are each identical, provided that R and R 3  are not hydrogen. 
     
     
       38. The compound of  claim 1  in which B is —CR 3 —, E is —CR 5 — and R 3  and R 5  are each identical, provided that R 3  and R 5  are not hydrogen. 
     
     
       39. The compound of  claim 1  in which B is —CR 3 —, D is —CR 4 —, E is —CR 5 —, J is —CR 14 —, K is —CR 8 — and R 3 , R 4 , R 5 , R 8  and R 14  are each hydrogen. 
     
     
       40. The compound of  claim 1  in which -D is —CR 4 —, E is —CR 5 —, G is CR 6 , J is —CR 14 —, K is —CR 8 — and R 4 , R 5 , R 6 , R and R 14  are each hydrogen. 
     
     
       41. The compound of  claim 1  which has the structural formula (Ia), (Ib), (Ic), (Id) or (Ie): 
       
         
           
           
               
               
           
         
       
       or a pharmaceutically acceptable salt, hydrate or solvate thereof, wherein X, Y, R 2 , R 6 , R 11  and R 12  are as previously defined for  claim 1  and - - - represents a single or double bond. 
     
     
       42. The compound of  claim 41  in which R 11  is hydrogen, R 12  is dichloromethyl and R 2  and R 6  are each, independently of one another, selected from the group consisting of fluoro, chloro, trifluoromethyl and methoxy. 
     
     
       43. The compound of  claim 1  which has the structural formula (If): 
       
         
           
           
               
               
           
         
       
       or pharmaceutically acceptable salt, hydrate or solvate thereof, wherein R 2 , R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 11 , R 12  and R 14  are as previously defined for  claim 1  and subject to the same provisos and - - - represents a single or double bond. 
     
     
       44. A compound which inhibits HCV replication and/or proliferation as measured in an in vitro assay, the compound selected from the group consisting of. 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
       45. A method of inhibiting replication or proliferation of a hepatitis C (“HC”) virion, comprising the step of contacting a HC virion with an amount of a compound of any one of  claims 1 – 12  effective to inhibit replication of the HC virion. 
     
     
       46. The method of  claim 45  which is practiced in vitro. 
     
     
       47. The method of  claim 45  which is practiced in vivo. 
     
     
       48. A method of inhibiting an HCV infection, comprising the steps of administering to a subject an effective amount of a compound of any one of  claims 1 – 12  effective to treat or prevent an HCV infection. 
     
     
       49. The method of  claim 48 , wherein the subject is a human. 
     
     
       50. The method of  claim 48 , wherein the compound is administered in an amount of 0.1 mg/kg to 200 mg/kg. 
     
     
       51. The method of  claim 48 , wherein the compound is administered in an amount of 10 mg/kg to 100 mg/kg. 
     
     
       52. The method of  claim 48 , wherein the compound is administered orally. 
     
     
       53. The method of  claim 48 , wherein the compound is administered by injection. 
     
     
       54. The method of  claim 48 , wherein the compound is selected from the group of compounds depicted in  FIG. 1  and which inhibits HCV replication and/or proliferation with an IC 50  of about 10 μM or less, as measured in an in vitro assay. 
     
     
       55. The method of  claim 48  which is practiced therapeutically in a subject having an HCV infection. 
     
     
       56. The method of  claim 48  which is practiced prophylactically in a subject at risk of developing an HCV infection. 
     
     
       57. A composition comprising a compound of any one of  claims 1 – 12  and a pharmaceutically acceptable vehicle.

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